Triazines



United States Patent 3,399,138 TRIAZINES Billy Dale Vineyard, St. Louis,Mo., assignor to Monsanto Company, St. Louis, Mo., a corporation ofDelaware No Drawing. Continuation-impart of application Ser. No.

502,405, Oct. 22, 1965. This application Oct. 11, 1967,

Ser. No. 674,656

7 Claims. (Cl. 25233.6)

ABSTRACT OF THE DISCLOSURE Lubricating oil compositions which exhibitdetergent properties by the incorporation into a lubricating oil ofcertain triazine compounds which can be derived from polyalkenylsuccinicacids and dicyandiamide. The lubricating oil compositions have many usesamong which are lubrication of internal combustion engines.

This application is a continuation-in-part of Ser. No. 502,405, filedOct. 22, 1965 and now abandoned.

This invention relates to certain novel triazines and to lubricating oilcompositions containing such triazines having improved detergentproperties.

Under the conditions encountered in a large percentage of present-dayautomobile driving (i.e., the so-called stopand-go driving), automobileengines do not attain their most desirable and eflicient operatingtemperatures. As a result, large quantities of oil-insoluble oxidationproducts are formed which eventually find their Way into the crankcase,Where they tend to build up on the internal parts of the engine,resulting in further inefficient engine operation. In present-daypractice, deposition of oxidation products is minimized by incorporatinginto lubricating oils metalcontaining detergents. The use ofmetal-containing detergents has not been totally satisfactory, however,since such detergents form ash deposits in the combustion chambers ofengines, fouling the spark plugs and creating other problems.Accordingly, it is the desire of those Working in the art to findsuitable detergents which are metal-free.

It has now been found that certain triazines are useful as metal-free orashless detergents in lubricating oil compositions. More particularly,the novel triazines of this invention, which are symmetrical1,3,5-triazines, can be represented by the structure NII OII where R isa polyalkenyl radical having a molecular weight of from about 800 toabout 2500, preferably from about 1100 to about 2000 and R is selectedfrom the group consisting of hydrogen, a hydrocarbon radical and aquaternary ammonium, Group I or Group II metal cation.

The new triazines of this invention can be prepared by reacting apolyalkenylsuccinic acid, represented by the structure 0 RCH( J o RH2-COOH where R and R have the aforedescribed significance, Withdicyandiamide (cyanoguanidine),

NH NHz-i'l-NH-CEN More particularly, the preferred method of preparationinvolves the steps of:

ice

(1) preparing a polyalkenylsuccinic anhydride by reacting maleicanhydride with an olefin polymer (e.g., polymers of ethylene, propylene,butylene, isobutylene and mixtures thereof) at temperatures of about 150C. to 250 C. in molar ratios of from about 1:1 to about 5:1,respectively,

(2) hydrolyzing the anhydride from Step 1 by heating it with water toform a polyalkenylsuccinic acid,

(3) reacting the acid from Step 2 with dicyandiamide while removing thewater of reaction to form the 1,3,5- triazines of this invention.

It has also been found, however, that Steps 2 and 3 can be combined tothe extent that dicyandiamide can be reacted with the anhydride fromStep 1 in the presence of water in an amount suflicient to initiate thereaction. This is possible probably because once the reaction isinitiated, water generated by the formation of triazines serves tohydrolyze the anhydride to acid. Of course, when Steps 2 and 3 arecombined, Water is not azeotropically removed as in Step 3. It is alsopreferred to conduct Step 3 in a water-immiscible hydrocarbon solvent inorder to reduce the amount of time involved to complete the reaction.Suitable hydrocarbon solvents are, for example, aromatic hydrocarbonssuch as benzene, toluene and xylene and aliphatic hydrocarbons. Inanalyzing the triazines of this invention, it has been found that minoramounts of other products are present but such products can be allowedto remain since they do not harmfully affect the detergent properties ofthe triazines.

The temperatures employed in Step 3 or combined Steps 2 and 3 range fromabout 50 C. to 60 C. and up, the speed of the reaction being dependentupon the temperatures used. As a practical matter, temperatures beyond200 C. would not be used. Preferably the reaction is conducted attemperatures on the order of C.-l50 C., such temperatures affording goodreaction rates. When R is a hydrocarbon radical it is preferred thatthere is present from 1 to about 30 carbon atoms and within this rangeit is more particularly preferred that the number of carbon atoms befrom about 1 to about 8 carbon atoms.

Typical examples of aliphatic radicals such as alkyl are methyl, ethyl,propyl, isopropyl, butyl, tert-butyl, amyl, hexyl, n-hexyl, sec-hexyl,2,2-dirnethyl-3 butyl, 2,2 dirnethy1-4-butyl, 2,3,-dimethyl-2-butyl,2-methyl-1-pentyl, 2-methy1-2-pentyl, 3-methyl-1-pentyl, 3-methyl-2-pentyl; heptyl, n-heptyl, sec-heptyl, 2,3-dimethyl-3-pentyl,2,4-dimethyl-2-pentyl, 2,4-dimethyl-3-pentyl-2,2,3 trimethyl-3- butyl,3-ethyl-2-pentyl, 2-methyl-2-hexyl; octyl, n-octyl, 2- ethylhexyl,diisobutyl, capril; nonyl, diisobutylcarbinyl, n-nonyl, decyl radicals,e.g., n-decyl, dodecyl radicals, e.g., lauryl, tetradecyl radicals,e.g., :myristyl, hexadecyl radicals, e.g., cetyl; octadecyl, alkylradicals having the formula C H where n is an integer from 18 to 38inclusive, e.g., those derived from paraflin wax, mineral oils andpetrolatum; alkenyl, examples of which are vinyl, propenyl radicals,e.g., allyl, isopropenyl; butenyl radicals, e.g., n-butenyl-l,n-butenyl-Z, n-buteny1-3, isobutenyl; pentenyl radicals, e.g.,n-pentenyl-l, n-pentenyl-Z, n-pentenyl-3; hexenyl radicals, e.g.,n-hexenyl-l, n-hexeny1-2, 4,4-dimethylbutenyl-2, 3,4 dimethylbutenyl 1,heptenyl radicals, e.g., n-heptenyl, octenyl radicals, n-octenyl,diisobutenyl, nonenyl radicals, e.g., n-nonenyl, decenyl radicals, e.g.,n-decenyl, dodecenyl radicals, e.g., n-dodecenyl, triisobutenyl;cycloaliphatic, examples of which are cycloalkyl radicals, e.g.,cyclopentyl, alkylated-cyclopentyl, cyclohexyl and alkylated-cyclohexylradicals, e.g., monoand polymethylcyclopentyl radicals, monoandpolymethylcyclohexyl radicals, monoand polyethylcyclohexyl radicals,monoand polyisopropylcyclohexyl radicals, monoandpoly-tert-amylcyclohexyl radicals, n-octylcyclohexyl radicals,diisobutylcyclohexyl (i.e., tert-octyl-cyclohexyl) radicals,nonylcyclohexyl radicals, diisoamylcyclohexyl radicals, laurylcyclohexylradicals, cetylcyclohexyl radicals, naphthenyl radicals, .hydrobietylradicals; cycloalkenyl radicals, e.g., cyclopentenyl,alkylated-cyclopentenyl, cyclohexenyl and alkylated-cyclohexenylradicals, e.g., monoand polymethylcyclopentenyl radicals, monoandpolymethylcyclohexenyl radicals, monoand polyethylcyclohexenyl radicals,monoand polyisopropylcyclohexenyl radicals, monoandpoly-tert-amylcyclohexenyl radicals, n-octylcyclohexenyl radicals,diisobutylcyclohexenyl. radicals, nonylcyclohexenyl radicals,diisoamylcyclohexenyl radicals, laurylcyclohexenyl radicals,cetylcyclohexenyl' radicals; dehydronaphthenyl radicals; abietylradicals; aryland cycloalkyl-substituted aliphatic radicals, e.g.,phenyland alkylphenyl-substituted alkyl radicals, e.g., benzylmethylbenzyl, caprylbenzyl, diisobutylbenzyl, phenylethyl, phenylpropyl,phenyloctadecyl; Xenyland alkylxeuyl-substituted alkyl radicals, e.g.,xenylmerthyl, caprylxenylmethyl, Xenylethyl, diisobutylxenylmethyl;naphthyland alkylnaphthyl-substituted alkyl radicals, e.g.,naphthylmethyl, tert-amylnaphthylmethyl, naphthylethyl,octylnaphthylethyl; cyclohexyland alkylcyclohexylsubstituted alkylradicals, e.g., cyclohexylethyl, methylcyclohexylethyl,ethylcyclohexylethyl, cyclohexylpropyl, tertamylcyclohexylbutyl;oxygen-containing aliphatic and cycloaliphatic radicals, e.g.,oxygen-containing aliphatic radicals, e.g., alkoXy-substituted alkylradicals, e.g., propoxyethyl radicals, e.g., n-propoxyethyl,isopropoxyethyl; butoxyethyl radicals, e.g., n-butoxyethyl,isobutoxyethyl, tert-butoxyethyl; octoxyethyl radicals, e.g.,n-octoxyethyl, diisobutoxyethyl; dibutoxypropyl radicals, e.g.,2,3-di-nbutoxypropyl, 3,3-diisobutoxypropyl; dioctoxypropyl, 2,3-bis(diisobutoxy)propyl; cycloalkoxy-substituted alkyl radicals, e.g.,cyclohexoxymethyl, cyclohexoxyethyl radicals, e.g.,beta-cyclohexoxyethyl, alphacyclohexoxyethyl; cyclohexoxybutyl radicals,e.g., 2-(cyclohexoxy)butyl, 2, 3-dicyclohexoxybutyl;methylcyclohexoxypropyl radicals, e.g., 2-(o-methylcyclohexoxy)propyl,2- (p-methylcyclohexoxy)propyl; butylcyclohexoxyethyl radicals, e.g.,betap-butylcyclohexoxy ethyl, alphasec-butylcyclohexoxy) ethyl;cyclopentoxyethyl radicals, e.g., alpha-cyclopentoxyethyl,betacyclopentoxyethyl; propylcyclopentoxymethyl radicals, e.g.,isopropylcyclopentoxymethyl radicals, n-propylcyclopentoxymethylradicals; alkenoxy-substituted alkyl radicals, e.g., propenoxyethylradicals, e.g., allyloxyethyl, isopropenoxyethyl; octenoxyethylradicals, e.g., diisobutenoxyethyl, dioctenoxypropyl radicals, e.g.,2,3-bis(diisobutenoxy)propyl; epoxyalkyl radicals, e.g., epoxypropyl,epoxybutyl radicals, e.g., 2,3-epoxy-n-butyl, 3,4-epoxy-n-butyl;carboalkoxyalkyl radicals e.g,, carbomethoxymethyl carboethoxyethyl,carbolauroxyethyl; aroxy-substituted alkyl radicals, for example,phenoxyand alkylphenoxysubstituted alkyl radicals, e.g., phenoxymethyl,phenoxyethyl, cetylphenoxyethyl, phenoxyphenethyl,caprylphenoxyphenethyl; oxygen-containing cycloaliphatic radicals, e.g.,alkoxy-, alkenoxyand aroxy-substituted cycloalkyl radicals, e.g.,alkoxy-substituted cyclopentyl radicals, e.g., monoandpolyethoxycyclopentenyl, octoxycyclopentyl radicals, e.g.,diisobutoxycyclopentyl; alkoxy-substituted cyclohexyl radicals, e.g.,monoand polymethoxycyclohexyl, octoxycyclohexyl radicals, e.g.,diisobutoxycyclohexyl, alkenoxy-substituted cyclopentyl radicals, e.g.,propenoxycyclopentyl radicals, e.g., allyloxycyclopentyl,isopropenoxycyclohexyl, octenoxycyclohexyl radicals, e.g.,diisobutenoxycyclohexyl; aroxy-substituted cyclopentyl s a 4 radicals,e.g., phenoxycyclopentyl, polyphenoxycyclopentyl radicals, e.g.,diphenoxycyclopentyl radicals, tetraphenoxycyclopentyl radicals,ethylphenoxycyclopentyl radicals, e.g., o-ethylphenoxycyclopentyl,p-ethylphenoxycyclopentyl, naphthoxycyclopentyl; amylnaphthylcyclopentylradicals, e.g., tert-amyl alpha-n-aphthoxycyclopentyl radicals,n-amyl-beta-naphthdxycyclopentyl radicals; aroxy substituted cyclohexylradicals, e.g., diphenoxycyclohexyl radicals, triphenoxycyclohexylradicals, butylphenoxycyclohexyl radicals, e.g., p-tert-butylphenoxycycloheXyl, n-butylphenoxycyclohexyl; naphthoxycyclohexyl radicals, e.g.,alpha-naphthoxycyclohexyl, beta-naphthoxycyclohexyl,methylnaphthoxycyclohexyl radicals; propylnaphthoxycyclohexyl radicals,e.g., isopropyl-alphanaphthoxycyclohexyl radicals,npropyl-beta-naphth0xycyclohexyl radicals; epoxycycloalkyl radicals,e.g., epoxycyclopentyl, epoxycyclohexyl; carboalkoxycycloalkyl radicals,e.g., carboethoxycyclopentyl, carbomethoxycyclohexyl,carbolauroxycyclohexyl; aliphatic and cycloaliphatic radicals containinginorganic elements, examples of which are halogens, metals, metalloids,e.g., selenium, silicon, sulfur; examples of such radicals are aliphaticradicals containing inorganic elements, e.g., alkyl radicals containinghalogen, e.g., Z-fluoroethyl, 2-chloroethyl, 2- iodoethyl; chloropentylradicals, e.g., 5-chloro-n-pentyl, 3,5-dichloro-n-octyl, alkenylradicals containing halogen, e.g., chloropropenyl radicals, e.g.,3-bromo-n-octyl, 3,4- dibromo-n-octyl; alkenyl radicals containinghalogen, e.g., chloropropenyl radicals, e.g., S-chloro-n-pentyl,3,5-dichloro-n-pentyl; bromooctyl radicals, e.g., 3 -bromo-noctyl,3,4-dibromo-n-octyl; alkenyl radicals containing halogen, e.g.,chloropropenyl radicals, e.g., 2-chloroallyl, chloroisopropenyl;bromobutenyl radicals, e.g., 4-bromocrotyl, 4,4-dibromocrotyl;chlorooctenyl radicals e.g., monoand polychlorodiisobutenyl; alkylradicals containing metal, e.g., radicals derived from metal alkoxides,e.g., MO-(CH M-O-(CH radicals derived from metal alkylcarboxylates,e.g.,

in which M represents one equivalent of a metal, examples of which arethe alkali metals, the alkaline earth metals, copper, silver, zinc,aluminum, cobalt, nickel, tin and lead; alkyl radicals containingsulfur, e.g.,

C H -Se-C H cycloaliphatic radicals containing inorganic elements, e.g.,cycloalkyland alkylatedcycloalkyl radicals containing halogen, e.g.,monoand polychlorocyclopentyl, monoand polychloromethylcyclohexyl, 4-tert-amyl-Z,6-dibromocyclohexyl, 4-capryl-2 fiuorocyclohexyl,4-diisohutyl-2 iodocyclohexyl; cycloalkenyland alkylated cycloalkenylradicals containing halogen, e.g., monoand polychlorocyclopentenyl,monoand polychloromethylcyclohexenyl, 4-tert-butyl-2-bromocyclohexenyl,4-capryl-2-fluorocyclohexenyl, 4-diisobutyl 2 iodocyclohexenyl;cycloalkyl radicals containing metal, e.g., radicals derived from metalcycloalkoxides; radicals obtained onthe removal of a hydrogen atom fromthe cycloaliphatic nucleus of, e.g., potassium cycloalkoxide ofpetroleum naphthenyl alcohol, lithium cycloalkoxide of hydroabietylalcohol; radicals derived from methyl cycloalkylcarboxylates, e.g.,

O GHQ-CH2 CHE-CH2 radicals obtained on the removal of a hydrogen atomfrom the cycloaliphatic nucleus of, e.g., sodium salt of petroleumnaphthenic acids, lithium salt of hydroabietic acid; cycloalkyl radicalscontaining sulfur, e.g.,

radicals obtained on the removal of a hydrogen atom from thecycloaliphatic nucleus of amyl thiolnaphthenate; aryl, herein defined toinclude mono-, diand polynuclear hydrocarbons, such as phenyl, naphthyland anthryl, typical examples of which are phenyl, cresyl, xylyl,mesityl, ethylphenyl, diethylphenyl, isopropylphenyl, n-propylphenyl,tert-butylphenyl, di-tert-butyphenyl, isobutylphenyl, n-butylphenyl,tert-amylphenyl, cyclohexylphenyl, methylcyclohexylphenyl, caprylphenyl,diisobuty-phenyl, laurylphenyl, cetylphenyl, paraflin wax-substitutedphenyl, nitrophenyl, monochlorophenyl, polychlorophenyl, e.g.,dichlorophenyl, trichlorophenyl, hydroxyphenyl, acetylphenyl,carbolauroxyphenyl, lauroxyphenyl, xenyl, monoand polychloroxenyl,caprylxenyl, phenoxyphenyl, thiophenoxyphenyl, diisobutylphenoxyphenyl,naphthyl, monoand polychloronaphthyl, cetylnaphthyl, anthracyl, monoandpolychloroanthracyl, phenanthryl, monoand polychlorophenanthryl,laurylphenanthryl,

MO--Ph-R- where M is one equivalent of a metal, Ph is the benzene ringand R is a divalent aliphatic radical, e.g., alkylene radicals, e.g.,methylene, ethylene, propylene; alkylhydroxyaryl radicals, e.g.,monomethylhydroxyphenyl radicals, polymethylhydroxyphenyl radicals,e.g., dimethylhydroxyphenyl radicals, trimethylhydroxyphenyl radicals;monoethylhydroxyphenyl radicals; polyethylhydroxyphenyl radicals;diethylhydroxyphenyl radicals, triethylhydroxyphenyl radicals;monobutylhydroxyphenyl radicals, e.g., tert-butylhydroxyphenyl radicals,sec-butylhydroxyphenyl radicals; polybutenylhydroxyphenyl radicals,e.g., di-tert-butylhydroxyphenyl radicals, monomethyldihydroxyphenylradicals; polymethyldihydroxyphenyl radicals, e.g.,dimethyldihydroxyphenyl radicals, trimethyldihydroxyphenyl radicals;monopropylhydroxynaphthyl radicals, e.g.,monoisopropyl-alpha-hydroxynaphthyl radicals; polypropylhydroxynaphthylradicals, e.g., di-n-propyl-beta-hydroxynaphthyl radicals;alkylchloroaryl radicals, e.g., methylmonochlorophenyl radicals,methylpolychlorophenyl radicals, e.g., methyldichlorophenyl radicals,methyltrichlorophenyl radicals; ethylmonochloroanthracyl radicals, e.g.,ethylmonochloro-alpha-anthracyl radicals,triethylmonochloro-beta-anthracyl radicals; ethylpolychloroanthracylradicals, e. g., ethyldichloro-alpha-anthracyl radicals,diethyltrichloro-beta-anthracyl radicals; alkylnitroaryl radicals, e.g.,methylnitrophenyl radicals, dimethylnitrophenyl radicals,ethyldinitrophenyl radicals, butylnitronaphthyl radicals, e.g.,tert-butylnitronaphthyl radicals, sec butyldinitronaphthyl radicals,propylnitrophenanthryl radicals, e.g., isopropyldinitrophenanthrylradicals, di-n-propyldinitrophenanthryl radicals, monoandpolyhydroxyphenyl, dialkylaminophenyl, monoand polyacylaryl, hydroxyandacyl-substituted aryl, cyanophenyl, alkylcyanophenyl,butylcyanonaphthyl, phenoxyphenyl, tert-butylphenoxyphenyl,dialkylaminophenyl and the like; and the aforedescribed groups furthersubstituted with a heterocyclic group containing from 4 to atomsoptionally interrupted by from 1 to 4 hetero atoms, which can benitrogen, sulfur or oxygen or combinations thereof, such as substitutedand unsubstituted pyridyl and the like. Typical examples of quaternaryammonium, Group I metal and Group II metal cations are ammonium,quaternary methyl ammonium, quaternary ethyl ammonium, quaternary propylammonium and quaternary alkyl ammonium cations wherein the alkyl grouphas from 1 to 18 carbon atoms, lithium, sodium, potassium and rubidium,magnesium, calcium, barium, zinc and cadmium and the alkaline earthmetal anions having a higher basicity than the neutral alkaline earthmetal salt. Examples of the higher basic salts formed from alkalineearth metals are those salts which are prepared by carbonating acompound of this invention wherein R is an alkaline earth metal in thepresence of an excess amount of an alkaline earth metal wherein aninorganic acidic material is passed through the reaction mass to producean overbased material. The term Group II metal ion wherein the Group IImetal is an alkaline earth encompasses generically these overbasedalkaline earth metal salts. The procedure that is utilized to preparethese overbased alkaline earth metal salts is Well illustrated by US.3,312,- 618 which illustrates various acidic materials which can beutilized such as carbon dioxide and the process conditions for preparingthe overbased compounds of this invention.

In naming the triazines of the present invention, the system has beenadopted of designating the approximate molecular weight of thepolyalkenyl radical by a number in parentheses after the name of thepolyalkenyl radical in a particular compound. Thus, typical examples ofthe triazines of this invention are:

2-[3-(2-polybutenyl (880) propionic acid)]-4-hydroxy-6-amino-l,3,5-triazine,

2-[3-(2-polyethenyl (1000) propionic acid)]-4-hydroxy-6-amino-1,3,5-triazine,

2-[3-(2-polypropenyl (about 980) propionic acid)]-4-hydroxy-6-amino-1,3,5-triazine,

2-[3-(2-polybutenyl (900) propionic acid)]-4-hydroxy-6-amino-1,3,S-triazine,

2-[3-(2-polybutenyl (1300) propionic acid)]-4-hydroxy-6-amino-1,3,5-triazine,

2-[3-(2-polybutenyl (1500) pnopionic acid)]-4-hydroxy-6-amino-1,3,5-triazine.

The preparation of typical 1,3,5-triazines of this invention isillustrated in the following non-limiting examples, wherein parts areparts by weight unless otherwise stated.

EXAMPLE 1 Into a suitable reaction vessel fitted with a mechanicalstirrer, heating mantle, thermometer, Dean-Stark trap and condenser,containing 304 parts of polybutneyl (980) succinic acid in xylene, thereis charged 19.7 parts of dicyandiamide and the resulting mixture isheated to reflux (about 145 C.) for about 6 hours, while azeotropicallyremoving the water of the reaction. Thereafter, the xylene is strippedunder vacuum to provide the product 2-[3-(2-polybutenyl (980) propionicacid)]-4-hydroxy-6-amino-1,3,5-triazine, which analyzed 3% nitrogen.

EXAMPLE 2 In the manner of Example 1, 2-[3-(2-polybutenyl (1300)propionic acid)]-4-hydroxy 6 amino 1,3,5- triazine is prepared byreacting 2-00 parts of polybutenyl (1300) succinic acid in toluene with9.2 parts of dicyandiamide at C. C. for 8 hours. The product analyzed2.52% nitrogen.

EXAMPLE 3 Into a suitable reaction vessel fitted as described in Example1 (except for the Dean-Stark trap), a mixture of 200 parts ofpolybutenyl (1350) succinic acid, 13.2 parts of dicyandiamide and 150cc. of xylene is heated at about 110 C. for approximately 9 hours, afterwhich the temperature is raised to 125 C. C. for about 2 hours, afterwhich time the reaction mixture is practically clear. Xylene is thenstripped under vacuum to leave the product 2-[3-(2-polybutneyl (1350)propionic acid)]-4-hydroxy-6-amino-1,3,5-triazine, which analyzed 3.1%nitrogen.

EXAMPLE 4 To a suitable reaction vessel fitted as described in Example 1having additionally a gas inlet tube and a gas exit tube is added 1160grams of the sodium salt of 2-[3- (2-polybutenyl (980)propionic acid)] 4hydroxy-6- amino-1,3,5-triazine. In 420 grams of n-propyl alcohol isadded 301 grams of barium oxide at a temperature of 60 to 100 C. Thetemperature is heated to reflux for one hour and is treated at this sametemperature for solution. The mixture is then heated to 125 C. at aretwo hours while passing carbon dioxide through the duced pressure of18 mm. and then filtered.

EXAMPLE 5 To a suitable reaction vessel fitted as described in Example 1having additionally a gas inlet tube and a gas exit tube is added 1480grams of the sodium salt of 2-[3- (Z-polybutenyl (1300) propionicacid)]-4 hydroxy-6- amino-1,3,5-triazine. In 420 grams of n-propylalcohol is added 301 grams of barium oxide at a temperature of 70 C. Thetemperature is heated to reflux for one hour and is treated at this sametemperature for two hours while passing carbon dioxide through thesolution. The mixture is then heated to 115 C. at a reduced pressure of14 mm. and then filtered.

EXAMPLE 6 To a suitable reaction vessel fitted as described in Example 1having additionally a gas inlet tube and a gas exit tube is added 1530grams of the sodium salt of 2-[3-(2-polybutenyl (1350) propionicacid)]-4hydroxy- 6-amino-l,3,5-triazine. In 420 grams of npropyl alcoholis added 301 grams of barium oxide at a temperature of 60 to 100 C. Thetemperature is heated to reflux for one and one-half hours and istreated at this same temperature for three hours while passing carbondioxide through the solution. The mixture is then heated to 125 C. at areduced pressure of 18 mm. and then filtered.

EXAMPLE 7 To a suitable reaction vessel is charged 200 parts of thetriazine compound of Example 1 diluted with 250 grams oi n-heptane. Tothis mixture is then charged 21 grams of sodium hydroxide in 100 ml. ofwater. The mixture is stirred at a temperature of 80 C. for a period ofthree hours. The temperature is then reduced to 25 C. and the productwashed three times with one liter of water. The solvent is then removedat a temperature of 70 C. at a reduced pressure of 5 mm.

The following products were prepared utilizing the procedure ofExample 1. These products together with the nitrogen-containing compoundused and the mole ratio of polybutenylsuccinic anhydride tonitrogen-containing group are given for Examples 8 through 16 in TableI.

TABLE I Mole Ratio Molecular Polybutenyl- Ex Weight ofNitrogen-Containing succinic N0 Polybutenyl Compound Anhydride to G roupNitrogen- Containing Group 980 Aminoguanidino 1:1 1,300 do 1:1 980 do2:1 080 N-n-butylguanid 1 1 980 N-dodocylguanidin 1 :2 980 N,N-di-mbut-ylguanidina 1: 1 J80 N-cyclohexylguanidino 1:1 080 Guanylurea 2: 1 J N-u-butyluroa l :1

8. Example 17 To a conventional glass reactor, fitted with an agitator,raw material inlet, product outlet, reflux, condenser, Dean-Stark. trap,heating means and thermometer is charged a mixture of 84 grams (160milliequalivalents) of a polyisobutene-substituted succinic anhydride(average molecular weight about 1050), 13.5 grams (0.16 mole) ofcyanoguanidine and 25 ml. of toluene. The temperature of the mixture ismaintained at the reflux temperature of toluene for a period of 14hours. Water is collected during the reflux period. The temperature isallowed to reach room temperature and the product is filtered. Thetoluene is stripped under vacuum and the product is diluted with 74grams of oil.

The triazines of this invention were tested for detergency effectivenessin lubricating oil formulations by screening in a test referred to asLacquer Deposition test. This test involves passing burned gasolinefumes through a sample formulation in a suitable container undercontrolled conditions, after which the sample is aged in an oven. Theamount of deposit is then determined after washing away the oil. Acontrol formulation is run simultaneously. The results are reported interms of percent reduction in deposits, which percent is determined bydividing the amount of deposits when a detergent is present by theamount of deposits when no detergent is present. The Lacquer DepositionTest has proved to be of great value since the results obtainedcorrelate extremely well with the results which are obtained in FL-2(CRC) test. Thus, since the triazines of this invention show very highdetergency in the Lacquer Deposition Tests, as will be noted fromreference to the table below, FL-2 tests using such triazines would beexpected to have total ratings of the order of -95 or higher. Utilizingthe above-described tests, the results presented in Table II, below wereobtained.

TABLE II Concentration of Example No. Reaction Product LTD Percent inLubricating Reduction Oil Compositions From the above, it is clear thatthe addition to lubricating oils of the triazines of the presentinvention brings with it a clear improvement of the dispersing and/ordetergent qualities of said oils.

In addition Table II clearly demonstrates that the triazine compounds asa class are far superior in effectiveness as detergents thancorresponding products derived from compounds having a similar structureto that of dicyandiamide, In particular, Table II demonstrates thatproducts derived from amino guanidine, dodecylguanidine and guanylureaare inferior in effectiveness when compared to the triazine compounds ofthis invention. In addition to the above, Table II demonstrates that themonotriazines of this invention have outstanding detergent performancewhen compared to a product formed by the reaction of two moles ofdicyandiamide with an alkenylsuccinic anhydride. Thus, Examples 3 and 17in Table II when compared demonstrate that the monotriazine compoundshave over 300% greater effectiveness than a product prepared asillustrated in Example 17. From the above, it is clear that themonotriazine compounds prepared from dicyandiamide clearly haveoutstanding detergent performance in comparison to other products whichare derived from similar nitrogen-containing compounds.

The triazines of this invention can be used in lubricating oilcompositions in amounts of from about 0.05% to about 25% by Weight, andin the case of additive concentrates, from about to about 85% by weight.It has been found, however, that for most applications, greatly improveddetergent-dispersant elfects can be obtained by the use in lubricatingoil compositions of amounts of from about 0.5% to about 10% by weight.The compounds of this invention can also be used in fuel oils andvarious light products such as gasoline wherein they also function asdetergents.

Lubricating oils which can be used as the base oils to which the newcompounds of this invention are added are not limited as far as thedetergent-dispersant effects are concerned, and, accordingly,lubricating oils which are of a naphthenic base, paraffinic base orother hydrocarbon base, as well as lubricating oils derived from coalproducts and synthetic oils, such as the alkylene polymers, alkyleneoxide polymers, olefin-chlorinated hydrocarbon polymers, dicarboxylicacid esters, alkylated benzenes, silicate esters, silicon polymers, andthe like, are suitable.

Since the greater part of the commercial lubricating oils sold today aresubject to a large number of uses, and it is, therefore, generallynecessary to employ more than one type of additive in a finishedlubricant composition. Thus, although the products of the presentinvention are effective detergentsdispersants, it is frequentlynecessary to use such products in combination with other types ofadditives, such as metal-containing detergents and/or dispersants,corrosion inhibitors, oxidation inhibitors, extreme pressure agents,viscosity index improvers, pour-point depressors, antifoaming agents,and the like.

A particularly useful combination of additives intended to be applied inmotor lubricants is the combination of an additive of the presentinvention and a metal-containing derivative of phosphorus such as ametal phosphorodithioate, e.g., zinc dihexyl phosphorodithioate, thezinc salt of mixed alkyl phosphorodithioates where the alkyl groups areobtained, for example, from an equal mixture of isobutyl and n-arnylalcohols, and the metal salts of phorphorus sulfide-olefin polymerreaction products and combinations thereof.

While this invention has been described with reference to variousspecific examples and embodiments, it is understood that the inventionis not limited thereto and that it can be variously practiced within thescope of the following claims.

What is claimed is:

1. A composition comprising a major amount of a lubricating oil and aminor amount of a triazine compound represented by the structure where Ris a polyalkenyl radical having a molecular weight of from about 800 toabout 2500 and R is selected from the group consisting of hydrogen, ahydrocarbon radical, a quaternary ammonium cation, Group I metal cationand a Group II metal cation.

2. A composition of claim 1 wherein R is a hydrocarbon radical havingfrom 1 to 30 carbon atoms.

3. A composition of claim 1 wherein R is a hydrocarbon radical havingfrom 1 to 8 carbon atoms.

4. A composition of claim 1 wherein R is a polyalkenyl radical havingfrom 1100 to 2000 molecular weight and R is hydrogen.

5. A composition of claim 1 wherein R is a polyalkenyl radical having amolecular weight of from 1100 to 1500.

6. A composition of claim 1 wherein R is selected from the groupconsisting of hydrogen, hydrocarbyl having from 1 to 8 carbon atoms anda Group II metal cation wherein the Group II metal is selected from thegroup consisting of calcium and barium.

7. A composition of claim 6 wherein the Group II metal cation has abacicity greater than the neutral Group II metal cation.

References Cited UNITED STATES PATENTS 3,219,666 11/1965 Norman et a1.25251.5 3,338,831 8/1967 Elliott et a1. 252 51.5

PATRICK P. GA-RVIN, Primary Examiner.

